Curable compositions comprising a tetraallylsulfonamide and a polythiol

ABSTRACT

The compounds:   and   in which: A. R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, fluorine, chloride, bromine, and lower alkyl; B. A is   c. R9 is   c. R9 is   an alkylene group having 2-20 carbon atoms, a cycloalkylene group having 3-10 carbon atoms, a phenylene group, an alkaryl group having 7-10 carbon atoms, or an aralkyl group having 7-10 carbon atoms; and D. R10 and R11 are independently selected from a group consisting of hydrogen, lower alkyl, a cycloalkyl group having 3-10 carbon atoms, a phenyl group, an alkylaryl group having 710 carbon atoms, and an aralkyl group having 7-10 carbon atoms.

United States Patent 11 1 Dighe et al.

[ Oct. 28, 1975 CURABLE COMPOSITIONS COMPRISING A TETRAALLYLSULFONAMIDEAND A POLYTHIOL [75] Inventors: Shrikant V. Dighe, Silver Spring;

Richard W. Bush, Columbia, both of Md.

W. R. Grace & Co., New York, N.Y.

[22] Filed: June 24, 1974 [21] Appl. No.: 482,734

Related US. Application Data [62] Division of Ser. No. 303,848, Nov. 6,1972, Pat. No.

[73] Assignee:

[52] US. Cl. 204/l59.23; 96/33;96/35.1; 96/36.3; 204/159.18; 204/159.24;260/47 UA; 260/49; 260/79; 260/79.3 R; 260/543 R; 260/556 AR; 260/612 R;427/54; 428/458;

' [51] Int. Cl. C08F 2/46; C08F 8/00 [58] Field of Search 260/550 AR, 47UA, 79.3; 204/l59.23, 159.18, 159.24; 96/115 P [56] References CitedUNITED STATES PATENTS 3,700,574 10/1972 Kehr et al. 204/l59.14 3,725,4764/1973 Blackwood et a1 260/556 AR Primary Examiner-Richard B. TurerAttorney, Agent, or Firm-Elton Fisher [5 7] ABSTRACT The compounds:

1, 2, R R R R R and R are independently selected from the groupconsisting of hydrogen, fluorine, chloride, bromine, and

5 Claims, No Drawings CURABLE COMPOSITIONS COMPRISING ATETRAALLYLSULFONAMIDE AND A POLYTHIOL CROSS REFERENCE TO RELATEDAPPLICATION This is a divisional of application Ser. No. 303,848, filedNov. 6, 1972, and now US. Pat. No. 3,856,858. The benefit of the filingdate of said earlier filed applio cation is hereby claimed.

BACKGROUND OF THE INVENTION aln alkylene group having 220 carbon atoms,a cy- I I coalkylene group having 3-10 carbon atoms, a Thls {nvennon f ito; N phenylene group, an alkaryl group having 7-10tetrallyldiphenylether-4,4 -d1sulfonamide (TADEDS); Carbon atoms or nralkyl group having 7-10 car- (b) a number of related sulfonamides; and(c) the prepbon atoms. aration of such sulfonamides fromdiphenylether-4,4'- d. Rm and 1 are independent] Selected from adisulfonyl chloride (DEDSC) or nuclear substituted group consigting ofhydrogen liwer alk 1 ac DEDSC and diallylamine. DEDSC is commerciallyalkyl group having 340 carbon atomsy phyen 1 available from NationalPolychemicals, Inc., Wilminggroup an alkylaryl grou havin Garb y ton,Mass, and 4,4-disulfonyl chlorides of substituted atoms and an aralky]gp g diphenylethers can be readily prepared by obvious conatoms g nventional methods including those recited hereinafter. In Speciallypreferred embodiments of the compound 7 of Embodiment A, supra: SUMMARYOF THE INVENTION 1 2 3 4 5. 6 5 8, R,.,, and R are hydro en. In summarythis invention is directed to a compound R2 R3 R R R R and R e R gh I 19 r a 5s 6r 7 8 'r 1 having the formula R are hydrogen and R is 1 R2 R5R5 HC=CHCH2 CH2CH=CH2 N05 0 SO N HZC=CHCHZ \CHCH=CHZ R4 R3 R5 R1 inwhich R R R R R R R and R are independently selected from the groupconsisting of hydrogen, fluorine, chlorine, bromine, and lower alkyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a preferred embodiment ofthe compound of the above Summary R R R R R R R and R are hydrogen.

In another preferred embodiment (Embodiment A) this invention isdirected to a compound having the formula R R R R, R, R R

ClO,S O A O- R/ R R R R R R in which:

a. R R R R R R and R are independently selected from the groupconsisting of hydrogen, fluorine, chloride, bromine, and lower alkyl;

b. A is c. R is 3. R through R are hydrogen, R and 11 are hydrogen, andR is R,, R,, R, R, R R, R,, R,, HC=CHCH2 /CH2CH=CH2 N025 O A O SON\H2C=CHCH, CH,CH=CH 7 a a 4 4 a s 1 in which: 3. R, through R,, arehydrogen, R is a. R,, R R,, R,,, R,,, R,,, R,, and R, are independentlyselected from the group consisting of hydrogen, fluorine, chloride,bromine, and lower alkyl;

b. A is RIO ll c. R,, is

an alkylene group having 2-20 carbon atoms, a cycloalkylene group having3-10 carbon atoms, a phenylene group, an alkaryl group having 7-10carbon atoms, or an aralkyl group having 7-l0 carbon atoms; and

d. R,,, and R,, are independently selected from a group consisting ofhydrogen, lower alkyl, a cycloalkyl group having 3-l0 carbon atoms, aphenyl group, an alkylaryl group having 7l0 carbon atoms, and an aralkylgroup having 7-10 carbon atoms.

In specially preferred embodiments of the compound of Embodiment B,supra:

l. R, through R,, are hydrogen. 2. R, through R,, are hydrogen, R,, is

and R,,, and R,, are hydrogen.

4. R, through R,, are hydrogen and R is an alkylene group having about2-12 carbon atoms.

5. R, through R,, are hydrogen and R,, CH (CH ).,CH

6. R, through R,, are hydrogen; R is -CH (CH ),C- H and R,,, and R,, arehydrogen.

ln another preferred embodiment (Embodiment C) this invention isdirected to a compound having the formula R R,, R R

R R R H l c in which R,, R R,,, R,, R R R and R,, are independentlyselected from the group consisting of hydrogen, fluorine, chlorine,bromine, and lower alkyl; or (2) in which:

a. R R R R R R R and R are independently selected from the groupconsisting of hydrogen, fluorine, chloride, bromine, and lower alkyl;

b. A is an alkylene group having 2-20 carbon atoms, a cycloalkylenegroup having 3-10 carbon atoms, a

phenylene group, an alkaryl group having 7-10 carbon atoms, or anaralkyl group having 7-10 carbon atoms; and

d. R and R are independently selected from a geoup consisting ofhydrogen, lower alkyl, a cycloalkyl group having 3-10 carbon atoms, aphenyl group, an alkylaryl group having 7-10 carbon atoms, and anaralkyl group having 7-10 carbon atoms; and

B. a liquid polythiol component having molecules containing at least twothiol groups per molecule.

In especially preferred embodiments of the composition of Embodiment D:

1. The curable composition contains a photocuring rate accelerator.

2. The photocurable rate accelerator is selected from the groupconsisting of aryl aldehyde, diaryl ketone, triaryl phosphine, and ablend of a carbon tetrahalide with a polynuclear aromatic hydrocarbon.

3. The photocuring rate accelerator is present in an effective amountfrom about 0.05 to about 25 percent by weight of the curablecomposition.

4. The composition contains a member of the group consisting of afiller, pigment, odor mask, lightscattering agent, plasticizer andanitoxidant in an effective amount equal to about 0.005 to about 500parts per 100 parts of the photocurable compositron.

DETAILED DESCRIPTION OF THE INVENTION The reaction of primary andsecondary amines with benzenesulfonyl chloride is well known to thoseskilled in the art and was used by Hinsberg to separate mixtures ofprimary, secondary, and tertiary amines. See; (a) Reynold C. Fuson,Organic Chemistry, Edwards Brothers, Inc., Ann Arbor, Mich., 1939, pp.216217; and (b) Ralph G. Shriner et al, The Systematic Identification ofOrganic Compounds, John Wiley & Sons, Inc., New York, N. Y., 1956, pp.103.

We have found that a modification of this reaction can be used toprepare polyenes having the formulas set forth in the above Summary andin Embodiment B, supra, and in the embodiments (number 1-6) listed undersaid Embodiment B which can then be reacted with a polythiol of the typetaught, described, and used in US. Pat. Nos. 3,535,193 (161/88, R. W.Prince) and 3,578,614 (260/13, W. R. Wszolek) to prepare offset printingblankets and curable compositions (useful as adhesives and for coatingsurfaces (e.g., wooden surfaces, soft metal surfaces, and the like) toprovide a coating which, after curing will protect the coated surfacesfrom the action of solvents, scratching, and the like.

We have also found that a modification of this reaction can be used toprepare compounds having the formulas set forth in Embodiment A, supra,and in the embodiments (the embodiments number 1-6) listed under saidEmbodiment A.

The instant invention will be better understood by referring to thefollowing specific but nonlimiting examples. It is understood that saidinvention is not limited by these examples which are offered merely asillustrations; it is also understood that modifications can be madewithout departing from the spirit and scope of the invention.

EXAMPLE 1 Materials: 36.7 g (0.1 mole), Diphenyl ether-4,4-disulfonylchloride 8.0 g (0.2 mole), Sodium hydroxide 20.0 g (0.2 mole),Diallylamine In a 500 ml., three-necked round bottom flask equipped witha reflux condenser, thermometer, addition funnel and a mechanicallydriven stirrer were placed 8.0 g of sodium hydroxide dissolved in 100 mlof water and 20.0 g of diallylamine. The resulting mixture was heated toC while stirring. Diphenyl ether disulfonyl chloride (DEDSC) dissolvedin 200 ml. of tetrahydrofuran was added dropwise from the funnel. Aftera few ml. of the solution had been added, the temperature rose to C. Atthis point heating was stopped and the rate of addition so adjusted asto maintain a temperature of 505 5C during addition. After the additionwas complete, the reaction mixture was refluxed for four hours and thenallowed to cool to room temperature. The cold solution separated intotwo layers. It was added to a large excess (ca. 1 liter) of water withvigorous stirring. A white precipitate separated; said precipitate wascollected on a filter and dried in vacuo at 50C. The thus dried materialwas recrystallized from tetrahydrofuran-pentane mixture.

The white recrystallized product melted sharply at 8586C and weighed42.5 g corresponding to a conversion (1 pass yield of 88% of theory).Said recrystallized product was identified as TADEDS by NMR (nuclearmagnetic resonance).

EXAMPLE 2 A composition was prepared by admixing TADEDS prepared as inExample 1, supra, with pentaerythritol tetrakis (3-mercaptopropionate)which is also known as pentaerythritol tetrakis (B-mercaptopropionate)in a mole ratio of 1:1 and incorporating into said mixture 2% by weightof benzophenone (based on the weight of the TADEDS). The resultingmixture was melted, admixed thoroughly, and spread over a thin metalsheet to form a thin film (ca. 15-20 mil thick). The resulting film wascooled to room temperature and exposed to the light of a 4,000 wattAscorlux pulsed xenon are printing lamp through a photographic negativehaving an image thereon. Exposure time was 2.6 minutes, the xenon lightbeing about 30 inches from the surface of the aforesaid resulting film.A cured image was present on the exposed areas of said resulting filmwhen said resulting film was developed by washing with a suitablesolvent (a mixture of acetone and water in a weight ratio of about 3parts acetone per part of water). The unexposed portions of saidresulting film were dissolved and washed away by the solvent while theexposed portions of said resulting film were not dissolved (and notwashed away) by said solvent. The resulting printing plate was mountedon a printing press using double-face pressure-sensitive tape andprinting was carried out in the same way conventional metalphotoengraved plates are employed. The printing results obtained weresuperior to those with conventional plates.

EXAMPLE 3 The general procedure of Example 2 was repeated, however, inthis instance the procedure was modified by dissolving the resultingmixture of TADEDS, pentaerythritol tetrakis (3-mercaptopropionate) andbenzophenone (after said resulting mixture had been melted and cooled)in acetone, applying a film of said acetone solution to a thin sheet ofmetal, and drying said film of acetone solution (i.e., freezing saidfilm of its acetone) to form a resulting film of the composition ofExample 2, (TADEDS plus pentaerythritol tetrakis (3-mercaptopropionate)plus benzophenone) having a thickness of about 15 mils on the surface ofthe metal sheet.

when this film of said composition was exposed to actinic light from theXenon are printing lamp (said light passing through a photographicnegative as in Example 2) and developed as in Example 2. The resultingprinting plate was mounted on a printing press using doublefacepressure-sensitive tape and printing was carried out in the same wayconventional metal photoengraved plates are employed. The printingresults obtained were supreior to those with conventional plates.

EXAMPLE 4 TADEDS (N,N,N,N-tetrallyldiphenylether-4,4'- disulfonamide)made by the procedure of Example 1 was admixed with pentaerythritoltetrakis (3-mercaptopropionate) in a mole ratio of 1:1 and 3% ofbenzophenone (based on the weight of the TADEDS) was added to themixture which was then melted, admixed thoroughly, cooled to roomtemperature, and designated Composition 4".

Composition 4 was dissolved in acetone and the resulting solution wasdesignated Composition 4-A.

Composition 4-A was coated on a fine-count laminated offset blanketcarcass composed of 3 layers of square weave 80 X 80 prestretched cottonfabric impregnated and adhered together with a butadieneacrylonitrilecombining compound. Lamination of the carcass took place under heat andpressure. The carcass was coated on a spreading apparatus equipped witha movable doctor blade which ran over the surface to be coated. Thecoated material was immobile on the support table. After the sheet wascoated, the doctor blade was moved out of the -way, and the coating wasdried (i.e., the acetone was evaporated therefrom). A dry (substantiallyacetone free) coating having a thickness of 0.020 inch resulted. Thethus formed dry coating was exposed to light of a 4,000 watt Ascorluxpulsed xenon are printing lamp made by the American Speed Light Corp.which was placed 30 inches above the surface. Total exposure given toall portions of the coated blanket was 2 minutes and 40 seconds, theactinic light having passed through a photographic negative. The thusexposed coating was developed by treating with a mixture of acetone andWater to remove uncured material and to form a fully developed offsetplate. Thereafter the blanket was removed from the apparatus, punched ateither end to receive blanket hooks and wrapped around the cylinder ofasmall offset printing press. The lithograph plate test copy was preparedwith ll densities ranging from full black to light gray. Each densitywas properly reproduced. Performance in all respects equaled aconventionally coated offset blanket.

EXAMPLE 5 Materials:

36.7 g (0.1 mole) DEDSC 4.0 g (0.1 mole) Sodium hydroxide 9.9 g (0.05mole) Methylene bis-aniline In a l-liter, three-necked, round bottomflask equipped with a condenser, thermometer, addition funnel, and amechanically driven stirrer were placed 4.0 g of sodium hydroxidedissolved in ml. of water and 9.9 g of methylene bis-aniline dissolvedin 100 ml. tetrahydrofuran. The stirred mixture was heated to 50C and asolution of 36.7 g DEDSC in 100 ml. tetrahydrofuran added dropwise atsuch a rate as to maintain a reaction temperature of 5055C. After theaddition was complete, the reaction mixture was refluxed for 1 hour andallowed to cool to room temperature. The cooled mixture was designatedMixture 5-A.

A small sample of the cooled mixture (Mixture S-A) was removed from thereaction flask, evaporated to dryness (i.e., until substantially free ofsolvent) under reduced pressure leaving a first residue. The firstresidue was extracted with a small quantity of dilute (ca. 2 molar)aqueous hydrochloric acid solution, leaving an extracted residue behind.The extracted residue was dried under reduced pressure leaving a secondresidue behind. This second residue was identified by NMR and by itsinfrared spectrum as in which; (a) R through R, are hydrogen; (b) A is(c) R is 6 5 R 1 H,C=CHCH N 8 0 H2C=CHCH/ R, R R R. 4

in which;

a. R through R were hydrogen; (b) A was In a l-liter, three-necked,round bottom flask equipped with a condenser, thermometer, additionfunnel, and a mechanically driven stirrer were placed 9.3 g ofhexamethylenediamine dissolved in 100 ml of tetrahydrofuran and 3.2 g ofsodium hydroxide dissolved in 100 ml of water. The stirred mixture washeated to 5055C. and 3.6 g of DEDSC dissolved in 100 ml oftetrahydrofuran was added dropwise to maintain the reaction temperatureat 55-60C. After the addition was complete, the reaction mixture wasrefluxed for 1 hour and allowed to cool to room temperature. The cooledmixture was designated Mixture 7-A".

A small sample of the cooled mixture (Mixture 7-A) was removed from thereaction flask, evaporated to dryness (i.e., until substantially free ofsolvent) under reduced pressure leaving a first residue. The firstresidue was extracted with a small quantity of dilute (ca. 2 molar)aqueous hydrochloric acid solution leaving an extracted residue behind.The extracted residue was dried under reduced pressure leaving a driedresidue CH CH=CH behind. This dried residue was identified by NMR and byits infrared spectrum as R R R R R. 1 a a CIO:S% 0%A O%SO CI R R R 4 R4a a 1 d. R and R were hydrogen.

EXAMPLE 6 EXAMPLE 7 c. R was Materials;

36.7g (0.] mole) DEDSC 9.3g (0.08 mole) Hexamethylenediamine 3.2g (0.08mole) Sodium Hydroxide in which;

a. R through R are hydrogen b. A is SO NR,NO,S

0. R is CH (CH CH and d. R and R are hydrogen. A solution of 1.6 g (0.04mole) of sodium hydroxide in 50 ml of water was added to Mixture 7-A inthe reaction flask. The resulting mixture in said flask was heated to5560C. Diallylamine (4 g, 0.04 mole) was added dropwise and theresulting reaction mixture refluxed for an hour, cooled to roomtemperature, added to 500 ml of water, and acidified with hydrochloricacid to pH 5-6 causing a white precipitate to form. The precipitate wasseparated by fiteration and dried under reduced pressure. The thus driedprecipitate, which was designated Product 7-B was identified by NMR andby its infrared spectrum as R R5 R: R, R. R-, R, R6 HC=CHCH2 /CH2CH=CH2NO-LS O A O SOZN\ H C=CHCH CH CH=CH, R, R R; R. R. a 3 1 in which; etherextract was dried with Drierite (anhydrous cal a. R through R werehydrogen; l0 cium sulfate). The resulting dried ether extract--a solub.A was tion of Compound 9-A in etherwas designated Fourth Mixture. 5.Said compound 9-A was recovered from the fourth mixture by distillingthe ethyl ether from the fourth mixture.

c. R is CH (CH CH and Compound 9-A was characterized and identified byd. R and R were hydrogen. elemental analysis and by its nuclear magneticreso- EXAMPLE 8 nance (NMR) and infrared spectra. The general procedureof Example 4 was repeated. Run 2: However, in this instance, the TADEDSof Example 4, Compound was Converted to C0mP0Und supra, was replacedwith Product 7-3 (from Example Said Compound 93 a g the f l 7, supra).The results were indistinguishable from those of Example 4.

CH, CH CH CH EXAMPLE 9 Run No. l: CIOZS 0 02C Preparation of Compound9-A, said compound having the formula CH; CH3 CH3 CH3 CH;, CH, CH3 CH3by reacting of the above-described compound 9-A with chlorosulfonic acidby slowly adding 0.2 mole said 0 Compound 9-A to 1 mole of cold (ca.0C.) chlorosulfonic acid while stirring the resulting mixture andmaintaining it at about 0C. The resulting mixture was maintained atabout 0C. for about 3 hours and then poured Several batches of theabove-identified Compound Over a kllogram of Crushed The resultmg com- 9A were p p y pound 9-B separated out. The separated Compound I Admixin 025 a of 2 3 5 6 tetrameth I henol 9-B was recovered and dried undervacuum at about and 1 mole 0% hiaOH (present as an aqueous s lution 50CCompound was Characterized and id.emified analyzing about 36% NaOH) in areaction flask having g j g analysxs and by its NMR and mfrared a refluxcondenser, an entrance port, and a mechanip cally driven stirrer. Waterwas added as necessary to R N 3;

l t l p g i g ggg :5: sg l 3 5 6 tetramethyl The general procedure ofRuns Nos. 1 and 2 of this benzene to the first mixture while stirringthe resulting Example r.epeated' However m .thls mstance P secondmixture and heating said second mixture to procedure used 1 was "i byreplacmg maintain a vigorous reflux-after refluxing for about 2 the.chlomsulfomc. acld Wnh a mlxmre of 1 mole of hours the second mixturewas cooled to about 25C fuming sulfuric acid (ca. 10% free SO content)and 1 3. A third mixture was formed by neutralizing the mole of PC15'resulting prciciuct ((;ompound 9J3) cooled second mixture with dilutehydrochloric acid was recovered dned and Identified as m Run 2. (ca. 6normal) using litmus paper as indicator. The third mixture was cooled toabout 15C. R N

4. The cooled third mixture was extracted with 9% its un volume of cool(ca. 15C.) ether (i.e., eth l th The general procedure of Example 1 wasrepeated. (C H OC H th th extracted thi d mixture was However, in thisinstance the procedure was modified extracted with a second portion ofcool ether, and the by replacing the DEDSC of Example 1 with Compound 2portions of ether extract were combined and washed -B from Run NO. 2 ofExample 9. The product Com with cool water (ca. 15C.) using about 1volume of pound 9-C"was identified by elemental analysis, NMR, water per5 volumes of ether extract. The thus washed and its infrared spectrum asin which R through R were each CH,-,. Table [-Cominued Run No. MaterialRun No. 5 4 HZN The general procedure of Example 2 was repeated.However, in this instance the TADEDS was replaced 5 H2N CHZCH2 NH2 withCompound 9-C from Run No.4 of Example 9. The results wereindistinguishable from those of Example 2. 10 6 H N CH CH NH H RunNo.6:7 HN NH The general procedure of Example 1 was repeated. H A However, inthis instance the procedure was modified a a by replacing the DEDSC ofExample 1 with Compound Z 9-B from Run No. 3 of Example 9. The productCompound 9-C" was identified by elemental analysis, NMR,

. 8 and its infrared spectrum as R R R R H C=CHCH, CH2CH==CH No.5 o SO,N

H2C=CHCH2 CH CH=CH R R R R,

in which R through R were each CH T 'h w Run No. 7: CH2 (3H2 The generalprocedure of Example 2 was repeated. 9 CH1 However, in this instance theTADEDS was replaced 3'5 with Compound 9-C from Run No. 6 of Example 9.The results were indistinguishable from those of Example 2.

HN-CH2CH,CH,NH

EXAMPLE 10 40 CH:

A series of runs was made using the general procedure of Example 5.However in each of these runs the methylene bisaniline was replaced withan equal molar amount of one of the materials listed in Table l, belowIn each instance a resulting intermediate compound (making at least onerun with each of said materials). h i h f l Table 1 Run No. Material R3R R R in which; (a) R1 through R were hydrogen; and (b) A was R wasphenylene and R and R were hydrogen and where the material in said tablewas R was -CH CH CH R was In each instance the intermediate was reactedwith diallylamine as in Example 5 to produce a product compound havingthe formula and R, was

in which R, through R were hydrogen and A, R R and R were the same as inthe intermediate compound from which the product compound was prepared.The intermediate and product compounds were identified by elementalanalysis and by their infrared and NMR spectra.

EXAMPLE 11 A series of runs were made using the general procedure ofExample 4. However, in these runs the procedure was modified byreplacing the TADEDS of Example 4 with the product compounds of Example10 (using one of said product compounds in each run). In

I each instance the results were indistinguishable from those of Example4.

EXAMPLE 12 A number of runs were made using the general procedure of RunNo. 1 of Example 9. However, in each of runs the 2,3,5,6-tetramethylphenol was replaced with a material listed in Column A of Table ll, andthe l-bromo-2,3,5,6-tetramethyl benzene was replaced with a materiallisted in Column B of Table II.

Table Ii Column A Column B OH Br F C3H1 Cl CH, Cl

In each instance the product was identified by elemental analysis, NMR,and its infrared spectrum as a compound (Compound l2-A) having theformula in which R R R and R corresponded to the function groups (otherthan -OH) of the compound (substituted phenol) selected from Column A ofTable II which was used to prepare the Compound l2-A and R R R and Rcorresponded to the functional groups (other than bromine) of thesubstituted bromobenzene selected from Column B of Table II which wasused to prepare the Compound l2-A.

A number of runs were made repeating the general procedure of Run No. 2Example 9. However, in each instance, the procedure was modified byusing a Compound l2-A selected from the above-prepared group ofcompounds which were designated Compound 12-A.

In each instance the resulting product was identified by elementalanalysis, NMR, and its infrared spectrum as a compound (Compound 12-8)having the formula 17 1s 1 2 R6 in which (a) R R R R R R R and R were asi in the Compound l2-B from which the particular Compound l5-A wasprepared; CIZS O SO Cl (b) A was R4 Ra a R1 IO u in which each of R,, RR R R R R and R was SC? N R N OZS; g Same g compourlid IZ'A from Whlchthe and (c) R R and R were determined by the mateompoun was prepare riallisted in Table I from which the particular Com- EXAMPLE 13 pound l5-Awas prepared. For example, where the ma- The general procedure ofExample 1 was repeated. tenal m Table I was However, in this instancethe procedure was modified 15 by making a series of runs in which thediphenyl ether- 4,4'-disulfonyl chloride of Example 1 was replaced NHwith a Compound l2-B from Example 12 (using one 2 Compound 12-8 in eachrun).

In each run the product (Compound l3-A) was identified by elementalanalysis, NMR, and its infrared R was phenylene and R and R werehydrogen and spectrum as when the material in said table was R R R RH2C=CHCH2 CH2CH=CHZ NO S 0 S02 H2C=CHCH2 \CH,CH=CH2 R R R R,

in which R,, R R R R R R and R were the HN CH,CH,--NH same as inCompound l2-B from which the Compound l3-A was prepared.

EXAMPLE 14 A series of runs was made using the general procedure ofExample 4. However in each of these runs the procedure was modified byreplacing the TADEDS R9 was with a Compound l3-A from Example 13 (usingone 40 R10 was Compound l3-A per run). In each instance the results ofthese runs were indistinguishable from those of Example 4.

EXAMPLE 15 A series of runs was made using the general proceand was dureof Example 5. However, in each of these runs the methylene bis-anilinewas replaced (on a mole for mole basis) with one of the materials listedin Table l and in each run the DEDSC was replaced (on a mole for molebasis) with a Compound l2-B prepared according to the procedure ofExample 12, supra, using one Compound l2-B in each run and makingsufficient runs to EXAMPLE insure that each Compound 12 -B was reactedwith A series of runs was made using the general proceeach of thematerials listed in said Table I. dure of Example 1. However in theseruns the proce- In each instance the resulting product was identifieddure was modified by replacing, in each instance, the by elementalanalysis, NMR, and its infrared spectrum DEDSC with an equal molaramount of a Compound as a compound (Compound l5-A) having the formulal5-A (using one Compound l5-A in each run and mak- 6 R5 R:' R. R. R2 R,R, c1o,s- E o E A- E o so,c1, R, R R R, R, R R R, and I v ing at leastone run with each Compound l-A).

In each instant the resulting product was identified by elementalanalysis, NMR, and its infrared spectrum as a compound (Compound l6-A)having the formula H2C=CHCH-,

N028 o o 7 n c=cncn R, R R3 R4 R and R are as in the particular Compound-A from which the particular Compound l6-A was prepared.

EXAMPLE 17 A series of runs were made using the general procedure ofExample 4. However, in each of these runs the procedure was modified byreplacing the TADEDS with an equal molar amount of a Compound l6-A. Ineach instance the results were indistinguishable from those obtained inExample 4.

In other runs using the general procedure of Examples 4 and 17 the moleratio of TADEDS (or the compounds recited in Embodiments B and theembodiments thereunder) to pentaerythritol tetrakis(3-mercaptopropionate) was varied over the range of l:0.8-l.2, andexcellent results were obtained in each instance.

In other runs using the general procedure of Examples 4 and 17 thepentaerythritol tetrakis (3-mercaptopropionate) was replaced with alarge number of polythiols having at least two -SH groups per moleculeand including ethylene glycol (B-mercaptopropionate), propylene glycol(B-mercaptopropionate), and the polythiols disclosed in US. Pat. No.3,615,450 (Werber et al, 96/351) the equivalent ratio of --CH =CH groupsof the TADEDS or a Compound l6-A to -SH groups varied over the range ofl:O.8-l.2. In each in stance the results were indistinguishable fromthose of Example 4.

In other runs using the general procedure of Examples 4 and 17 thebenzophonone was replaced with the UV sensitizers (photoinitiators)recited in the aforesaid Werber et al patent and the amounts of saidphotointiators recited in said Werber et al patent. In each instance theresults were indistinguishable from those of Examples 4 and I7.

In still other runs the general procedures of Examples 4 and 17 wererepeated. However in these runs the fillers of the aforesaid Werber etal patent (in the quantities taught by said patent) were incorporatedinto and admixed with the mixtures of TADEDS and polythiol (or Compoundl6-A and polythiol) before applying said mixtures to the laminatedoffset blanket carcasses. In each instance the results wereindistinguishable from those of Example 4.

In other runs using the general procedure of Example 4 and Example 17the procedure was modified by incorporating into and admixing with themixtures of TADEDS and polythiol (or Compound 16-A and polythiol) thepigments, odor masks, light-scattering agents, plasticizers andantioxidants of said Werber et al patent in the quantities taught bysaid patent. In each instance the results were substantiallyindistinguishable from those of Example 4.

20 We have found that radiation (light) having a wavelength of2000-4000A is excellently adapted for curing compositions comprisingTADEDS and a polythiol (or a Compound l6-A and a polythiol).

In another series of runs the general procedure of Examples 4 and 17were repeated. However in each of these runs the benzophenone wasomitted and the acetone solution of TADEDS and pentaerythritol tetrakis(3'mercaptopropionate) or the acetone solution of a Compound l6-A andpentaerythritol (3-mercapotpropionate) was applied to an aluminumsurface and, after drying (evaporating the acetone therefrom), cured byradiation with a high energy ionizing radiation (an electron beam). Theeffective radiation dosage used were O.5-30 megarads preferably 2-10megarads. The cured coating was a hard protective coating firmly bondedto the metal.

In other instances the electron beam was replaced with; (a) an X-raybeam; and (b) a beam of neutrons. Both the X-ray beam and the beam ofneutrons at dosage levels of 05-30 megarads gave a hard protectivecoating of cured polymer firmly bonded to the alumi num surface.

In another series of runs the general procedure of Examples 4 and 17were repeated. However in each of these runs the benzophenone wasomitted and the acetone solution of TADEDS and pentaerythritol tetrakis(3-mercaptopropionate) or the acetone solution of a Compound l6-A andpentaerythritol (3-mercaptopropionate) was admixed with an amount of aperoxide catalyst effective to produce crosslinking and coated onto analuminum surface. The acetone was evaporated therefrom, and in eachinstance the coating cured forming a hard protective coating firmlybonded to the Lupersol 224 (a commercially available peroxide catalyst),and Lupersol 256 (a commercially available peroxide catalyst). Ingeneral about 2% (based on the weight of the resulting mixture(exclusive of acetone)) of peroxide catalyst was used but excellentresults were obtained with larger and small amounts of catalyst.

Thus compositions comprising TADEDS and a polythiol or a Compound l6-Aand a polythiol or a composition containing a compound equivalent toTADEDS and a thiol (or a composition containing a compound equivalent toany one of our above-described Compound l6-A) is a free radical curablecomposition. We prefer to refer to our free radical curable compositionsas curable compositions. The free radicals for curing such compositionscan be generated by actinic light (preferably having a wave length ofca. 200-4000A), by high energy ionizing radiation, or by a free radicalgenerating peroxide.

As used herein, the term lower alkyl group means an alkyl group having1-7 carbon atoms. 5

As used herein, the term mole" has its generally acu us As used herein,the term 3 means gram (or grams). The term mil, as used herein, means0.001 inch. The term percent as used herein, means parts per hundred,and the term parts means parts by weight unless otherwise defined whereused.

The term ml as used herein means milliliter (0.001

liter).

As applied to TADEDS or to any Compound 16-A the term equivalent" meansthat quantity of TADEDS or CH=CH group (i.e., 27.0 g of the CH=CHgroup); 1/4 mole of TADEDS or a Compound 16-A is an equivalent of TADEDSor the Compound 16-A.

said Compound 16-A which contains one As applied to a polythiol the termequivalent means that quantity of the polythiol which contains one SHgroup (i.e., 33.1 g of SH group); 5 mole of pentaerythritol tetrakis(3-mercaptopropionate) is an equivalent, and 54; mole oftrimethylol-propane tris (thioglycolate) is an equivalent.

We claim:

l. A curable composition consisting essentially of an intimate mixtureof;

A. a compound having the formula;

in which;

c. R is an alkylene group having 2-20 carbon atoms, a cycloalkylenegroup having 3-10 carbon atoms, a phenylene group, an alkaryl grouphaving 7-10 carbon atoms, or an aralkyl group having 7-10 carbon atoms;and I d. R and R are independently selected from a group consisting ofhydrogen, lower alkyl, a cycloalkyl group having 3-10 carbon atoms, aphenyl group, an alkylaryl group having 7-10 carbon atoms, and anaralkyl group having 7-10 carbon atoms; and B. a liquid polythiolcomponent having molecules containing at least two thiol groups permolecule, the equivalent ratio of CH=CH to SH being l:0.8-l.2.

2. The composition of claim 1 in which the curable composition containsa photocuring rate accelerator.

3. The curable composition of claim 2 in which the photocurable rateaccelerator is selected from the group consisting of aryl aldehyde,diaryl ketone, triaryl phosphine, and a blend of a carbon tetrahalidewith a polynuclear aromatic. hydrocarbon.

CH2CH=CH,

clam-cu, R, R,

photocurable composition.

1. A CURABLE COMPOSITION CONSISTING ESSENTIALLY OF AN INTIMATE, MIXTUREOF, A. A COMPOUND HAVING THE FORMULA,
 2. The composition of claim 1 inwhich the curable composition contains a photocuring rate accelerator.3. The curable composition of claim 2 in which the photocurable rateaccelerator is selected from the group consisting of aryl aldehyde,diaryl ketone, triaryl phosphine, and a blend of a carbon tetrahalidewith a polynuclear aRomatic hydrocarbon.
 4. The curable composition ofclaim 2 in which the photocuring rate accelerator is present in aneffective amount from about 0.05 to about 25 percent by weight of thecurable composition.
 5. The curable composition of claim 2 in which saidcomposition contains a member of the group consisting of a filler,pigment, odor mask, light-scattering agent, plasticizer and antioxidantin an effective amount equal to about 0.005 to about 500 parts per 100parts of the photocurable composition.